The present invention relates to 2,2,6-trimethyl-1-cyclohexen-1-ylacetaldehyde (or "beta-cyclohomocitral") produced by, interalia, a novel process described and claimed in copending Application for U.S. Pat. No. 507,414 filed on Sept. 19, 1974 now U.S. Pat. No. 3,956,393 and copending application for U.S. Pat. No. 3,980,708, and novel compositions using such beta-cyclohomocitral to impart, alter, modify, or enhance the flavor and/or aroma of tobacco and tobacco flavoring compositions.
There has been considerable work performed relating to substances which can be used to impart (or alter, modify, or enhance) flavors and fragrances to (or in) tobacco. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product. Sweet, rich-tobacco, floral, fruity, green, woody, "damascenone-like" and earthy notes are desirable in tobacco flavoring compositions.
Arctander, "Perfume and Flavor Chemicals", 1969 discloses the use in perfume compositions and flavors of "cyclocitral", "dehydro-beta-cyclocitral", "isocyclocitral", "alphacyclocitrylidene acetaldehyde" and "beta cyclotrylidene acetaldehyde", thus:
I. "760: CYCLOCITRAL PA0 Alpha-cyclocitral = (2,2,6-trimethyl-5-cyclohexen-1-carboxaldehyde). PA0 ii. "761; iso-CYCLOCITRAL A mixture of two chemicals: 3,5,6-trimethyl-3-cyclohexen-1-carboxaldehyde (meta-cyclocitral). ##STR5## 2,4,6-trimethyl-4-cyclohexen-1-carboxaldehyde (symmetric-iso-cyclocitral). ##STR6## Powerful, and diffusive, foliage-green, "dark" weedy and dry odor, sometimes described as "Flower-shop odor". The earthy and wet-green notes are quite natural in high dilution and resemble the odor of stems from plants and flowers fresh from the soil. PA0 iii. "762: alpha CYCLOCITRYLIDENE ACETALDEHYDE ##STR7## Mild, floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity to the odor of hydrogentated Ionones. PA0 iv. "763: beta-CYCLOCITRYLIDENE ACETALDEHYDE 2,6,6-trimethyl-1-cyclohexenyl-beta-acrolein. ##STR8## Sweet-woody, rather heavy odor, resembling that of beta-Ionone. More fruity than really floral, but not as tenacious as the Ionone. PA0 V. "869" dehydro-beta-CYCLOCITRAL (Safranal) 2,6,6-trimethyl-4,4-cyclohexadiene-1-carboxaldehyde ##STR9## Very powerful, sweet, green-floral and somewhat tobacco-herbaceous odor of good tenacity. In extreme dilution reminiscent of the odor of Safran (Saffron). PA0 i. Reacting beta-ionone having the formula: ##STR12## in the absence of dimethyl formamide with a peralkanoic acid having the formula: ##STR13## (wherein R is hydrogen, methyl or ethyl) to form beta-ionone enol ester having the formula: ##STR14## and not the expected beta-ionone epoxide having one of the formulae: ##STR15## ii. hydrolyzing the beta-ionone enol ester in the presence of base (aqueous or alcoholic) to form beta-cyclohomocitral. PA0 A. where peralkanoic acids are used as the oxidizing agents, the reaction is preferably carried out in the presence of a buffer such as an alkali metal salt of a lower alkanoic acid or an alkali metal carbonate with a lower alkanoic acid such as propionic acid, acetic acid or formic acid with the following provisos:
Beta-cyclocitral = (2,2,6-trimethyl-6-cyclohexen-1-carboxaldehyde). Both isomers are known and have been produced separately. ##STR4## Very rarely offered commercially. These particular cyclocitrals have little or no interest to the creative perfumer, but they have served as part of many pieces of proof that isomers (alpha-beta) do often have different odors."
Finds use in perfume compositions where it blends excellently with Oakmoss products (compensates for sweetness and lifts the topnote), with Ionones (freshness), Geranium and Galbanum (enhances the green and "vegetable" notes), etc. ...."
Suggested for use in perfume compositions. It brings a certain amount of floral lift to Rose compositions, and performs fairly well even in soap. However, the cost of the rarely offered and never readily available lots and rather discouraging to the perfumer, and it is most conceivable that this material can be left out of the perfumer's library without any great loss. ..."
Suggested for use in perfume compositions, but since it does not offer any new or unusual odor characteristics, and it cannot be produced in economical competition to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer. ..."
Interesting material for fresh topnotes, as a modifier for aldehydic-citrusy notes, as a green-floral topnote in flower fragrances, etc. It blends excellently with the aliphatic Aldehydes, with Oakmoss products and herbaceous oils. ..."
Safranal and beta-cyclocitral are disclosed as volatile constituents of Greek Tobacco by Kimland et al., Phytochemistry 11 (309) 1972. Beta-cyclocitral is disclosed as a component of Burley Tobacco flavor by Demole aand Berthet, Helv. Chim. Acta. 55 Fasc-6, 1866 (1972).